Reaction product of certain acylated nitrogen containing intermediates and a boron compound



United States Patent REACTION PRODUCT OF CERTAIN ACYLATED NITROGENCONTAINING INTERMEDIATES AND A BORON COMPOUND William M. Le Suer,Cleveland, Ohio, assignor to The Lubrizol Corporation, Wickliife, Ohio,a corporation of Ohio No Drawing. Filed Apr. 29, 1963, Ser. No. 276,214

7 Claims. (Cl. 260-3263) This application is a continuation-in-part ofco-pending application Ser. No. 132,305, filed August 18, 1961, now US.3,087,936.

This invention relates to oil-soluble nitrogenand boron-containingcompositions and to the process of preparing the same. The compositionsof this invention are useful as additives in lubricants, especiallylubricants intended for use in internal combustion engines, gears, andpower transmitting units.

One of the principal problems associated with present day automobilecrankcase lubricants is that posed by the inevitable presence in thelubricant of foreign particles such as dirt, soot, water, anddecomposition products resulting from breakdown of the lubricating oil.Even if there were none of this latter contaminant present the verynature of the design of the modern internal combustion engine is suchthat a significant amount of foreign matter will accumulate in thecrankcase. Perhaps the most important of these contaminants is waterbecause it seems to be responsible for the deposition of amayonnaise-like sludge. It appears that if there were no water presentthe solid components of the mayonnaise-like sludge would circulate withthe oil and be removed by the oil filter. It will be readily appreciatedthat the deposition of the sludge presents a serious problem withrespect to the efficient operation of the engine and that it isdesirable to prevent such deposition of sludge-like material.

The presence of water and the precursors of sludge in a lubricating oilis dependent largely upon the operating temperature of the oil. If theoil is operated at a high temperature the water, of course, will beeliminated by evaporation about as fast as it accumulates. In theabsence of water as stated above the other foreign particles will beremoved by the filter. At low oil temperatures, on the other hand, waterwill accumulate and so consequently will sludge. It is apparent that theenvironment in which a crankcase lubricant is maintained will determineto a large extent the ultimate performance of that lubricant.

High operating temperatures are characteristic of a lubricant in anengine that is run at relatively constant high speed. Thus, in an enginethat is run at 60 miles per hour for a long period of time it is veryunlikely that there will be any accumulation of water and it issimilarly unlikely that there will be any formation and deposition ofsludge, but in ordinary stop-and-go driving such as is the case withtaxicabs, delivery trucks, police cruisers, etc., the crankcaselubricant will be alternately hot and cold, an ideal environment for theaccumulation of water. In such cases the formation of sludge is aserious problem. This problem has been with the automotive industry formany years and its solution has been approached by the use of knowndetergents such as metal phenates and sulfonates but without notablesuccess. Although such known detergents are very effective in solvingthe detergency problems associated iwth motor oils at high temperaturesthey have not been particularly effective in solving the problemsassociated with low temperature operation or, to put it better, thoseproblems which are associated with crankcase lubricants in engines whichare operated at alternating high and low temperatures.

3,281,428 Patented Oct. 25, 1966 It is accordingly a principal object ofthis invention to provide novel compositions of matter.

It is also an object of this invention to provide compositions which areadapted for use as additives in hydrocarbon oils.

It is also an object of this invention to provide compositions which areeffective as detergents in lubricating compositions.

It is another object of this invention to provide a novel process forthe preparation of products which are effective as dispersants inlubricant compositions.

It is another object of this invention to provide novel compositionswhich are effective dispersants in lubricant compositions intended foruse in engines operated at alternating high and low temperatures.

It is another object of this invention to provide improved hydrocarbonoil compositions.

It is another object of this invention to provide improved lubricatingcompositions.

It is another object of this invention to provide improved fuelcompositions.

These and other objects are achieved in accordance with this inventionby providing a process for preparing oil-soluble, nitrogenandboron-containing compositions comprising forming an acylated nitrogenintermediate by the reaction of a substantially hydrocarbon-substitutedsuccinic acid-producing compound having at least about 50 aliphaticcarbon atoms in the substantially hydrocarbon-substituent with at leastabout one-half equivalent of an amido compound having the formulawherein R is selected from the class consisting of hydrogen andhydrocarbon radicals and R is selected from the class consisting ofamino, cyano, carbamyl, and guanyl radicals and reacting said acylatednitrogen intermediate with a boron compound selected from the classconsisting of boron oxide, boron halides, boron acids, ammonium salts ofboron acids, and esters of boron acids in an amount to provide fromabout 0.1 atomic proportion of boron for each mole of said acylatednitrogen intermediate to about 10 atomic proportions of boron for eachatomic proportion of nitrogen of said acylated nitrogen intermediate.

The substantially hydrocarbon-substituted succinic acid-producingcompounds from which the acylated nitrogen intermediates of the aboveprocess are derived are characterized by the presence within theirmolecular structure of a substantially hydrocarbon group having at leastabout 50 aliphatic carbon atoms and at least one succinic acid-producinggroup. They are illustrated by compounds having the structural formulawherein R is a substantially hydrocarbon radical having at least about50 aliphatic carbon atoms and X is a halogen, hydroxy, hydrocarbon-oxy,or acyloxy radical.

The substantially hydrocarbon substituent of the succinic acid-producingcompounds may contain polar groups provided, however, that the polargroups are not present in proportions sufiiciently large to altersignificantly the hydrocarbon character of the substituent. The polargroups are exemplified by chloro, bromo, keto, ethereal, aldehydo, andnitro, etc. The upper limit with respect to the proportion of such polargroups in the substituent is approximately 10% based on the weight ofthe hydrocarbon portion of the substituent.

The sources of the substantially hydrocarbon substituent includeprincipally the high molecular weight substantially saturated petroleumfractions and substantially saturated olefin polymers, particularlypolymers of monoolefins having from 2 to 30 carbon atoms. The especiallyuseful polymers are the polymers of l-amino-olefins such as ethylene,propene, l-butene, isobutene, l-hexene, l-octene, Z-methyl-l-heptene,3-cyclohexyl-l-butene, and 2-methyl- -propyl-l-hexene. Polymers ofmedial olefins, i.e., olefins in which the olefinic linkage is not atthe terminal position, likewise are useful. They are illustrated byZ-butene, 3-pentene, and 4-octene.

Also useful are the interpolymers of the olefins such as thoseillustrated above with other interpolymerizable olefinic substances suchas aromatic olefins, cyclic olefins, and poly-olefins. Suchinterpolymers include, for example, those prepared by polymerizingisobutene with styrene; isobutene with butadiene; propane with isoprene;ethylene with piperylene; isobutene with chloroprene; isobutene withp-methyl styrene; l-hexene with 1,3-hexadiene; l-octene with l-hexene;l-heptene with l-pentene; 3-methyll-butene with l-octene;3,3-dirnethyl-l-pentene with l-hexene; isobutene with styrene andpiperylene; etc.

The relative proportions of the mono-olefins to the other monomers inthe interpolymers influence the stability and oil-solubility of thefinal products derived from such interpolymers. Thus, for reasons ofoil-solubility and stability the interpolymers contemplated for use inthis invention should be substantially aliphatic and substantiallysaturated, i.e., they should contain at least about 80%, preferably at.least about 95%, on a weight basis of units derived from the aliphaticmonoolefins and no more than about 5% of olefinic linkages based on thetotal number of carbon-to-carbon covalent linkages. In most instances,the percentage of olefinic linkages should be less than about 2% of thetotal number of carbon-to-carbon covalent linkages.

Specific examples of such interpolymers include copolymer of 95% (byWeight) of isobutene with 5% of styrene; terpolymer of 98% of isobutenewith 1% of piperylene and 1% of chloroprene; terpolymer of 95% ofisobutene with 2% of l-butene and 3% of l-hexene; terpolymer of 80% ofisobutene with 20% of l-pentene and 20% of l-octene; copolymer of 80% ofl-hexene and 20% of l-heptene; terpolymer of 90% of isobutene with 2% ofcyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20%of propene.

Another source of the substantially hydrocarbon radical comprisessaturated aliphatic hydrocarbons such as highly refined high molecularweight white oils or synthetic alkanes such as are obtained byhydrogenation of high molecular weight olefin polymers illustrated aboveor high molecular weight olefinic substances.

The use of olefin polymers having molecular weight of about 7505000 ispreferred. Higher molecular weight olefin polymers having molecularweights from about 10,000 to about 100,000 or higher have been found toimpart also viscosity index improving properties to the final productsof this invention. The use of such higher molecular weight olefinpolymers often is desirable.

The substantially saturated, aliphatic hydrocarbon-substituted succinicacids and anhydrides are especially preferred for use as theacid-producing reactant of this process for reasons of the particulareffectiveness of the products obtained from such compounds as additivesin hydrocarbon oils. The succinic compounds are readily available fromthe reaction of maleic anhydride with a high molecular weight olefin ora chlorinated hydrocarbon such as the olefin polymer describedherein-above. The reaction involves merely heating the two reactants ata temperature about 100-200 C. The product from such as reaction is analkenyl succinic anhydride. The alkenyl group may be hydrogenated to analkyl group. The anhydride may be hydrolyzed by treatment with water orsteam to the corresponding acid. Either the anhydride or the acid may beconverted to the corresponding acid halide or ester by reaction with,e.g., phosphorus halide, phenols, or alcohols.

In lieu of the olefins or chlorinated hydrocarbons, other hydrocarbonscontaining an activating polar substituent, i.e., a substituent which iscapable of activating the hydrocarbon molecule in respect to reactionwith maleic acid or anhydride, may be used in the above-illustratedreaction for preparing the succinic compounds. Such polar substituentsmay be illustrated by sulfide, disulfide, nitro, mercaptan, bromine,ketone, or aldehyde radicals. Examples of such polar-substitutedhydrocarbons include polypropene sulfide, di-polyisobutene disulfide,nitrated mineral oil, di-polyethylene sulfide, brominated polyethylene,etc. Another method useful for preparing the succinic acids andanhydrides involves the reaction of itaconic acid with a high molecularweight olefin or a polar-substituted hydrocarbon at a temperatureusually within the range from about C. to about 200 C.

The acid halides of the succinic acids can be prepared by the reactionof the acids or their anhydrides with a halogenation agent such asphosphorus tri-bromide, phosphorus pentachloride or thionyl chloride.The esters of such acids can be prepared simply by the reaction of theacids or their anhydrides with an alcohol or a phenolic compound such asmethanol, ethanol, octadecanol, cyclohexanol, phenol, na'phthol,octylphenol, etc. The esterification is usually promoted by the use ofan alkaline catalyst such as sodium hydroxide or sodium alkoxide or anacidic catalyst such as sulfuric acid. The nature of the alcoholic orphenolic portion of the ester radical appears to have little influenceon the utility of such ester as reactant in the process describedhereinabove.

The amido compounds from which the acylated nitrogen intermediates ofthe process of this invention are derived have the structural formulawherein R is a hydrogen or hydrocarbon radical and R is selected fromthe class consisting of amino, cyano, carbamyl, and guanyl radicals. ItWill be noted that because of the character of the R radical compoundsof the above formula are not amines. They are referred to as amidocompounds for the reason that they contain the radical. The R group ofthe formula is either hydrogen or a hydrocarbon radical having less thanabout 8 aliphatic carbon atoms such as an alkyl radical or analkylphenyl radical in which the alkyl group is illustrated by methyl,ethyl, isopropyl, tertiary-butyl, n-pentyl, isooctyl, cyclohexyl,cyclopentyl, Z-methylcyclohexyl, or n-heptyl radical. The R radical mayfurther be a phenyl-substituted alkyl radical such as Z-phenylethylradical or 4-phenylbutyl radical.

The R radical of the above formula is illustrated by: amino radical(i.e., R N), cyano radical (ie., NC), carbamyl or thiocarbamyl (i.e., RNC(=X)-, wherein X is either oxygen or sulfur), or guanyl radical (i.e.,R NC(=NR)-; R NN(R)C(=NR); or NC--N(R)C( NR)) (R being as is definedpreviously). It will be noted that where R is an amino radical the amidocompound is a hydrazine; where R is a cyano radical, the amido compoundis a cyanamide; where the R radical is a carbamyl radical, the amidocompound is a urea (or thiourea); and where the R radical is a guanylradical, the amido compound is a guanidine.

Specific examples of the amido compounds include: hydrazine,phenylhydrazine, N,N- diphenylhydrazine, N,N-diphenylthydrazine,N,N-dihexylhydrazine, cyanamide, dicyandiamide, dimethyl cyanamide,diethyl cyanamide, diallyl cyanamide, diisopropyl cyanamide, dioctylcyanamide, urea, thiourea, N,N'-dimethyl-urea,

N,N-dimethyl-urea, phenyl-urea, hexyl-urea, N,N-dioctyle-urea,phenyl-thiourea, N,N'-diphenyl-thiourea, guanidine,1,1-dimethylguanidine, 1,3-dimethylguanidine, 2- cyclohexy-lguanidine,l-aminogu-anidine, l-cyanoguanidine, 1,2-dicyanoguanidine, biguanide,l-phenylbiguanide, l-cyoloh-exylbiguanide, l-(o-toluyl)biguanide, etc.

The process of forming the acylated nitrogen intermediate by reactingthe substantially hydrocarbon substituted succinic acid-producingcompound with the amido compound is usually carried out by heating amixture of the acid-producing compound and the amido compound at atemperature above about 80 C., preferably within the range from about100 C. to about 250 C. However, when an acid or anhyd-ride is employed,the process often may be carried out at a lower temperature such as roomtemperature. The use of a solvent such as benzene, toluene, naphtha,mineral oil, Xylene, n-hexane, or the like is often desirable in theabove process to facilitate the control of the reaction temperature.

The relative proportions of the acid-producing compound and the amidoreactant to be used in the above process are such that at least aboutonehalf of a stoichiometrically equivalent amount of the amido react-antis used for each equivalent of the acid-producing compound used. In thisregard it will be noted that the equivalent weight of the amido reactantis based upon the number of the nitrogen atoms. Similarly the equivalentweight of the acid-producing compound is based upon the number of theacid-producing radicals defined by the structural configuration Thus,urea has two equivalents per mole; amino guanidine has four equivalentsper mole; a succinic acid or ester has two equivalents per mole, etc.

The upper limit of the useful amount of the amido reactant appears to beabout 1 mole for each equivalent of the acid-producing compound used. Onthe other hand, the lower limit is about one-half equivalent of theamido reactant used for each equivalent of the acidproducing compound.In most instances, the preferred amount of the amido reactant is fromabout 1 to 3 equivalents for each equivalent of the acid-producingcompound.

The boron compounds useful in reaction with the acylated nitrogenintermediate include boron oxide, boron oxide hydrate, borontrifluoride, boron tribromide, boron trichloride, HBF boron acids suchas boronic acid (e.g., alkyl-B(OH) or aryl-B(OH) boric acid, (i.e., H BOtetraboric acid (i.e., H2B5O7), metaboric acid (i.e., HBO ammonium saltsof such boron acids, and esters of such boron acids. The use ofcomplexes of a boron trihalide with ethers, organic acids, inorganicacids, or hydrocarbons is a convenient means of introducing the boronreactant into the reaction mixture. Such complexes are known and areexemplified by boron trifluoridediethyl ether, boron trifluoride-phenol,boron trifluoridephosphoric acid, boron trichloride-chloroacetic acid,boron tribromide-dioxane, and boron trifluoride-methyl ethyl ether.

Specific examples of boronic acids include methyl boronic acid,phenyl-boronic acid, cyclohexyl boronic acid, p-heptylphenyl boronicacid and dodecyl boronic acid.

The boron acid esters include especially mono-, di-, and tri-organicesters of boric acid with alcohols or phenols such as, e.g., methanol,ethanol, isopropanol, cyclohexanol, cyclopentanol, l-octanol, 2-octanol,dodecanol, behenyl alcohol, oleyl alcohol, stearyl alcohol, benzylalcohol, Z-butyl cyclohexanol, ethylene glycol, propylene glycol,trimethylene glycol, 1,3-butanediol, 2,4- hexanediol,1,2cyclohexanediol, 1,3-octanediol, glycerol, pentaerythritol,diethylene glycol, carbitol, Cellosolve, triethylene glycol,tripropylene glycol, phenol, naphthol, p-

butylphenol, o,p-diheptylphenol, n-cyclohexylphenol, 2,2- bis-(p-hydroxyphenyl) propane, polyisobutene (molecular weight ofl500)-substituted phenol, ethylene chlorohydrin, o-chlor-ophenol,m-nitrophenol, 6-bromo-octanol, mnitrophenol, 6-bromo-octanol, and7-keto-decanol. Lower alcohols, 1,2-glycols, and 1,3-glycols, i.e.,those having less than about 8 carbon atoms are especially useful forpreparing the boric acid esters for the purpose of this invention.

Methods for preparing the esters of boron acid are known and disclosedin the art (such as Chemical Reviews pages 9591064, volume 56). Thus,one method involves the reaction of boron trichloride with 3 moles of analcohol or a phenol to result in a tri-organic borate. Another methodinvolves the reaction of boric oxide with an alcohol or a phenol.Another method involves the direct esterification of tetra boric acidwith 3 moles of an alcohol or a phenol. Still another method involvesthe direct esterification of boric acid with a glycol to form, e.g., acyclic alkylene borate.

The ammonium salts of boron acids include principally the salts of boricacid with ammonia or lower alkyl amines, i.e., mono-, di-, or tri-alkylamines having less than 12 carbon atoms in each alkyl radical. Salts ofammonia or such amines with any other boron acid illustrated above arealso useful. It is often desirable to use a mixture of an ammonium saltand at least a molar amount of water. Water tends to cause at least apartial hydrolysis of the salt so as to liberate a boron acid. Thus, theuse of a mixture of an ammonium salt and water in many instances is anexpedient method of introducing a boron acid into the reaction mixture.Specific examples of the ammonium salts are ammonium salt of boric acid;a mixture of one mole of ammonium salt of boric acid and three moles ofwater; a mixture of one mole of monomethylamine salt of boric acid andone mole of Water; trimethylamine salt of boric acid;di-cyclo-hexylamine salt of boric acid, etc.

The reaction of the acylated nitrogen intermediate with the boroncompounds can be effected simply by mixing the reactants at the desiredtemperature. The use of an inert solvent is optional although it isoften desirable, especially when a highly viscous or solid reactant ispresent in the reaction mixture. The inert solvent may be a hydrocarbonsuch as benzene, toluene, naphtha, cyclohexane, n-hexane, or mineraloil. The temperature of the reaction may be varied within wide ranges.Ordinarily it is preferably between about 50 C. and about 250 C. In someinstances it may be 25 C. or even lower. The upper limit of thetemperature is the decomposition point of the particular reactionmixture.

The reaction is usually complete within a short period such as 0.5 to 6hours. After the reaction is complete, the product may be dissolved inthe solvent and the resulting solution purified by centrifugation orfiltration if it appears to be hazy or contain insoluble substances.Ordinarily the product is sufliciently pure so that further purificationis unnecessary or optional.

A desirable mode of carrying out the process for the preparation of theoil-soluble, nitrogenand boron-containing compositions consists inpreparing a solution or slurry of the boron reactant such as boric acidin a hydrocarbon solvent such as mineral oil or toluene and adding theacylated nitrogen intermediate to this solution or slurry. The principaladvantage of this particular method is the more efficient utilization ofthe boron reactant in the process. Another advantage is that theresulting mineral oil solution of the product is more readily filterablein the event that filtration becomes necessary to remove haze orinsoluble contaminants. The yield of the desired product is often higherthan that characteristic of the alternative methods of adding the boronreactant to the acylated nitrogen intermediate.

The reaction of the acylated nitrogen intermediate with the boroncompounds results in a product containing boron and nitrogen. It isbelieved that the reaction results in the formation of a complex betweenboron and nitrogen. Such complex may involve in some instances more thanone atomic proportion of boron with one atomic proportion of nitrogenand in other instances more than one atomic proportion of nitrogen withone atomic proportion of boron. The nature of the complex is not clearlyunderstood. Evidence appears to indicate that the complex results from adirect linkage between boron and nitrogen and that in most instances,the radicals originally present on the boron and the nitrogen atoms donot take part directly in the complex formation. However, in the case ofa boron acid as the reactant, the reaction is often accompanied with theformation of water.

Inasmuch as the precise stoichiometry of the complex formation is notknown, the relative proportions of the reactants to be used in theprocess are based primarily upon the consideration of utility of theproducts for the purposes of this invention. In this regard, usefulproducts are obtained from reaction mixtures in which the reactants arepresent in relative proportions as to provide from about 0.1 atomicproportion of boron for each mole of the acylated nitrogen intermediateused to about 10 atomic proportionss of boron for each atomic proportionof nitrogen of said acylated nitrogen intermediate used. The preferredamounts of reactants are such as to provide from about 0.5 atomicproportion of boron for each mole of the acylated nitrogen intermediateto about 2 atomic proportions of boron for each atomic proportion ofnitrogen used. To illustrate, the amount of a boron compound having oneboron atom per molecule to be used with one mole of an acylated nitrogenintermediate having five nitrogen atoms per molecule is within the rangefrom about 0.1 mole to about 50 moles, preferably from about 0.5 toabout 10 moles. The atomic proportion may be defined by a mathematicalequation such as the following 1 gram-atomic-proportion= Molecularweight of the compound in grams Number of the atoms of the element inquestion in the molecular structure of the compound The followingexamples are illustrative of the process for preparing the nitrogenandboron-containing compositions of this invention.

Example 1 A polyisobutenyl succinic anhydride is prepared by thereaction of a chlorinated polyisobutene with maleic anhydride at 200 C.The polyisobutenyl radical has an average molecular weight of 850 andthe resulting alkenyl succinic anhydride is found to have an acid numberof 113 (corresponding to an equivalent weight of 500). To a mixture of544 grams of this anhydride, 283 grams of mineral oil and 281 grams oftoluene there is added 30 grams of urea at 45 C. The resulting mixtureis heated at 130-135 C. for 11 hours whereupon 2.5 cc. of water isdistilled off. The residue is then heated to 140 C./ 20 mm. andfiltered. The filtrate has a nitrogen content of 1%. A mixture of boricacid and the above filtrate in relative proportions such as to provideone atomic proportion of boron per atomic proportion of nitrogen isheated at 150 C. for 3 hours and filtered. The filtrate is found to havea boron content of 0.2%.

Example 2 An acylated nitrogen intermediate is obtained by heating amixture of 1000 grams of the polyisobutene substituted succinicanhydride of Example 1, 159 grams of cyanoguanidine and 233 grams oftoluene at the reflux temperature for 14 hours while 7.15 grams of wateris removed by azeotropic distillation. The mixture is diluted with 740grams of mineral oil and toluene is then removed by heating the mixtureto 150 C. The residue is filtered and the filtrate has a nitrogencontent of 4.74%.

8 A mixture of this filtrate and boric acid in relative proportions suchas to provide one atomic proportion of boron per atomic proportion ofnitrogen is heated at C. for 3 hours and filtered at this temperature.The filtrate is an oil solution of the nitrogenand boron-containingcomposition having a nitrogen content of 4.1% and a boron content of3.1%

Example 3 A product is obtained by the procedure of Example 1 exceptthat urea is replaced with amino-guanidine on a nitrogen equivalentbasis.

Example 4 A product is obtained by the procedure of Example 1 exceptthat urea is replaced with phenyl biguanide (i.e., C HNHC(=NH)NHC(=NH)NH on a nitrogen equivalent basis.

Example 5 A product is obtained by the procedure of Example 1 exceptthat the urea is replaced with hydrazine hydrate on a nitrogenequivalent basis.

Example 6 A product is obtained by the procedure of Example 1 exceptthat urea is replaced with N,N-dibutyl thiourea on a nitrogen equivalentbasis.

Example 7 A product is obtained by the procedure of Example 1 exceptthat urea is replaced with N,N-diphenyl guanidine on a nitrogenequivalent basis.

Example 8 A product is obtained by the procedure of Example 1 exceptthat urea is replaced with guanyl-urea on a nitrogen equivalent basis.

Example 9 A mixture of a polyisobutene (molecular weight of1000)-substituted succinic anhydride (555 grams, 1 equivalent) andguanidine carbonate (60 grams, 2 equivalents) in 412 grams of mineraloil is heated at 150 C. for 6 hours and then blown with nitrogen at 180C. for 3.5 hours. The residue is cooled to 100 C. and mixed with boricacid (107 grams, 5.2 equivalents). The resulting mixture is heated at150 C. for 2 hours and C. for 1 hour and then filtered. The filtrate hasa nitrogen content of 2.3% and a boron content of 1.4%.

The nitrogenand boron-containing products of this invention are usefulfor a wide variety of purposes including pesticides, plasticizers,rust-inhibiting agents for treatment of metals, corrosion-inhibitingagents, extreme pressure agents, anti-wear agents, and detergents.

A principal utility of such products is as additives in lubricants. Ithas been discovered in accordance with this invention that when used forsuch purpose the effectiveness of the nitrogenand boron-containingproducts to impart a specific property to a lubricant is closely relatedto the size of the substantially hydrocarbon substituent in the succinicradical of the acylated nitrogen composition from which such productsare derived. More particularly it has been found that products in whichthe substantially hydrocarbon substituent contains more than about 50aliphatic carbon atoms are effective to impart oxidation-inhibiting,corrosion-inhibiting, and detergent properties to a lubricant. It hasalso been found that the detergent properties of the products diminishsharply with a decrease in the size of the substantially hydrocarbonsubstituent having less than about 50 aliphatic carbon atoms so thatproducts having less than about 35 aliphatic carbon atoms in thissubstituent are ineffective as detergent additives in lubricants.

The lubricating oils in which the compositions of this invention areuseful as additives may be of synthetic,

animal, vegetable, or mineral origin. Ordinarily mineral lubricatingoils are preferred by reason of their availability, general excellence,and low cost. For certain applications, oils belonging to one of theother three groups may be preferred. For instance, synthetic polyesteroils such as didodecyl adipate and di-Z-ethylhexyl sebacate are oftenpreferred as jet engine lubricants. Normally the lubricating oilspreferred will be fluid oils, ranging in viscosity from about 40 SayboltUniversal seconds at 100 F. to about 200 Saybolt Universal seconds at210 F.

The concentration of the nitrogenand boron-containing compositions asadditives in lubricants usually ranges from about 0.1% to about 10% byweight. The optimum concentrations for a particular application dependto a large measure upon the type of service to which the lubricants areto be subjected. Thus, for example, lubricants for use in gasolineinternal combustion engines may contain from about 0.5 to about of theadditive, whereas lubricating compositions for use in gears and dieselengine-s may contain as much as or even more of the additive.

This invention contemplates also the presence of other additives in thelubricating compositions. Such additives include, for example,supplemental detergents of the ashcontaining type, viscosity indeximproving agents, pour point depressing agents, anti-foam agents,extreme pressure agents, rust-inhibiting agents, and supplementaloxidation and corrosion-inhibiting agents.

The ash-containing detergents are exemplified by oilsoluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, or organic phosphorus acids characterized by at leastone direct carbon-to-phosphorus linkage such as those prepared by thetreatment of an olefin polymer (e.g., polyisobutene having a molecularweight of 1000) with a phosphorizing agent such as phosphorustrichloride, phosphorus heptasulfide, phosphorus pentasulfide,phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,or phosphorothioic chloride. The most commonly used salts of such acidsare those of sodium, potassium, lithium, calcium, magnesium, strontium,and barium.

The term basic salt is used to designate the metal salts wherein themetal is present in stoichiometrically larger amounts than the organicacid radical. The commonly employed methods for preparing the basicsalts involves heating a mineral oil solution of an acid with astoichiometric excess of a metal neutralizing agent such as the metaloxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperatureabout 50 C. and filtering the resulting mass. The use of a promoter inthe neutralization step to aid the incorporation of a large excess ofmetal likewise is known. Examples of compounds useful as the promoterinclude phenolic substances such as p'henol, naphthol, alkylphenol,thiophenol, sulfurized alkylphenol, and condensation products offormaldehyde with a phenolic substance; alcohols such as methanol,2-propanol, octyl alcohol, Cellosolve, :carbitol, ethylene glycol,stearyl alcohol, and cyclohexyl alcohol; amines such as aniline,phenylenediamine, phenothiazine phenyl-beta-naphthylamine, anddodecylamine. A particularly effective method for preparing the basicsalts comprises mixing an acid with an excess of a basic alkaline earthmetal neutralizing agent, a phenolic promoter compound, and a smallamount of water and carbonating the mixture at an elevated temperaturesuch as 60-200 C.

The preparation of a basic sulfonate detergent is illustrated asfollows: A mixture of 490 parts (by weight) of a mineral oil, 110 partsof water, 61 parts of heptylphenol, 340 parts of barium mahoganysulfonate, and 227 parts of barium oxide is heated at 100 C. for 0.5hour and then to 150 C. Carbon dioxide is then bubbled into the mixtureuntil the mixture is substantially neutral.

10 The mixture is filtered and the filtrate found to have a sulfate ashcontent of 25%.

The preparation of a basic barium salt of a phosphorus acid isillustrated as follows: A polyisobutene having a molecular weight of50,000 is mixed with 10% by weight of phosphorus pentasulfide at 200 C.for 6 hours. The resulting product is hydrolyzed by treatment with steamat 160 C. to produce an acidic intermediate. The acidic intermediate isthen converted to a basic salt by mixing with twice its volume ofmineral oil, 2 moles of barium hydroxide and 0.7 mole of phenol andcarbonating the mixture at 150 C. to produce a fluid product.

Furthermore, the oil-soluble, nitrogenand boron-containing compositionsof this invention have the unique effectiveness in enhancing the extremepressure and corrosion-inhibiting properties of a certain class ofadditives employed to impart these properties to a lubricant. Morespecifically, the additives which are so benefited are metaldithiocarbamates, xanthates, the Group II metal phosphorodithioates andtheir epoxide adducts, hindered phenols, sulfurized cyclalkanes,di-alkyl polysulfides, sulfurized fatty esters, phosphosulfurized fattyesters, alkaline earth metal salts of alkylated phenols, dialkylphosphites, triaryl phosphites, and esters of phosphorodithioic acids.

The Group II metal phosphorodithioates are the salts of acids having theformula in which R and R are substantially hydrocarbon radicals. Themetals for forming salts are exemplified by barium, calcium, strontium,zinc, and cadmium. The barium and zinc phosphorodithioates areespecially preferred. The substantially hydrocarbon radicals in thephosphorodithioic acid are preferably low or medium molecular weightalkyl radicals and alkylphenyl radicals, i.e., those having from about 1to about 30 carbon atoms in the alkyl group. Illustrative alkyl radicalsinclude methyl, ethyl, isopropyl, isobutyl, n-butyl, sec-butyl, thevarious amyl alcohols, n-hexyl, methylisobutyl carbinyl, heptyl,2-ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl, etc.Illustrative lower alkylphenyl radicals include butylphenyl, amylphenyl,di-amylphenyl, octylphenyl, etc. Cycloalkyl radicals likewise areusefuland these include chiefly cyclohexyl and the lower alkyl-cyclohexylradicals. Other substantially hydrocarbon radicals likewise are usefulsuch as tetra-decyl, octadecyl, eicosyl, butylnaphthyl, hexylnaphthyl,octylnaphthyl, cyclohexylphenyl, naphthenyl, etc. Many substitutedhydrocarbon radicals may also be used, e.g., chloropentyl,dichlorophenyl, and dichlorodecyl.

The availability of the phosphorodithioic acids from which the Group IImetal salts of this invention are prepared is well known. They areprepared by the reaction of phosphorus pentasulfide with an alcohol orphenol. The reaction involves four moles of the alcohol or phenol permole of phosphorus pentasulfide, and may be carried out within thetemperature range from about 50 C. to about 200 C. Thus the preparationof 0,0- di-n-hexyl phosphorodithioic acid involves the reaction ofphosphorus pentasulfide with four moles of n-hexyl alcohol at about C.for about 2 hours. Hydrogen sulfide is liberated and the residue is thedefined acid. The preparation of the zinc or barium salt of this acidmay be effected by reaction with zinc oxide or barium oxide. Simplymixing and heating these two reactants is sufiicient to cause thereaction to take place and the resulting product is sufficiently purefor the purposes of this invention.

Especially useful Group II metal phosphorodithioates can be preparedfrom phosphorodithioic acids which in turn are prepared by the reactionof phosphorus pentasulfide with mixtures of alcohols. The use of suchmixtures enables the utilization of cheaper alcohols which in themselvesdo not yield oil-soluble phosphorodithioic acids. Thus a mixture ofisopropyl and hexyl alcohols can be used to produce a very effective,oil-soluble metal phosphorodithioate. For the same reason mixtures ofsimple phosphorodithioic (i.e., acids prepared from one alcohol) acidscan be reacted with zinc oxide or barium oxide to produce lessexpensive, oil-soluble salts.

Another class of the phosphorodithioate additives contemplated for usein the lubricating compositions of this invention comprises the adductsof the metal phosphorodithioates described above with an epoxide. Themetal phosphorodithioates useful in preparing such adducts are for themost part the zinc phosphorodithioates. The epoxides may be alkyleneoxides or arylalkylene oxides. The arylalkylene oxides are exemplifiedby styrene oxide, p-ethylstyrene oxide, alpha-methylstyrene oxide,3-betanaphthyl-l,3-butylene oxide, m-dodecylstyrene oxide, andp-chlorostyrene oxide. The alkylene oxides include principally the loweralkylene oxides in which the alkylene radical contains 6 or less carbonatoms. Examples of such lower alkylene oxides are ethylene oxide,propylene oxide, 1,2-butene oxide, trimethylene oxide, tetramethyleneoxide, butadiene monoepoxide, 1,2-hexene oxide, and propyleneepichlorohydrin. Other epoxides useful herein include, for example,butyl 9,10-epoxy-stearate, epoxidized soya bean oil, epoxidized tungoil, and epoxidized copolymer of styrene with butadiene.

The adduct may be obtained by simply mixing the phosphorodithioate andthe epoxide. The reaction is usually exothermic and may be carried outwithin wide temperature limits from about C. to about 200 C. Because thereaction is exothermic it is best carried out by adding one reactant,usually the epoxide, in small increments to the other reactant in orderto obtain convenient control of the temperature of the reaction. Thereaction may be carried out in a solvent such as benzene, mineral oil,naphtha, or n-hexane.

The chemical structure of the adduct is not known. More than one mole,sometimes as many as four moles, of the epoxide can be made to combinewith the phosphorodithioate to form products useful herein. However,adducts obtained by the reaction of one mole of the phosphorodithioatewith from about 0.25 mole to about 1 mole of a lower alkylene oxide,particularly ethylene oxide and propylene oxide, have been found to beespecially useful and therefore are preferred.

The hindered phenols are those in which the carbon atoms at both orthopositions to the phenolic group contain substantially large substituentsso as to cause hinderence of the phenolic group. The common substituentsare the secondary and tertiary alkyl radicals such as isopropyl,tert-butyl, tert-pentyl, sec-pentyl, cyclohexyl, and tert-octylradicals. They likewise may be aryl radicals or large polar radicalssuch as bromo or nitro radicals. Examples of the hindered phenolsinclude 2,6-di-sec-butylphenol, 2,4-di-tert-butylphenol,2,6-di-tert-octyl-4-sec-pentylphenol, 2-tert-pentyl-6-tert-hexylphenol,2-tert-butyl-6-cyclohexyl-6-heptylphenol, 4,4-bis-methylene-2,6-di-tert-butylphenol 4,4'-methylene-bisZ-tert-butyl-6-sec-butylphenol) 2,4-dimethyl-6-tert-butylphenol,2,6-di-tert-butyl-6-methylphenol, andbis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide.

The sulfurized esters of the fatty acids are obtained by the treatmentof the esters with a sulfurizing agent such as sulfur or a sulfurhalide, e.g., sulfur monochloride or sulfur dichloride. The esters areexemplified by methyl oleate, methyl stearate, allyl stearate, isopropylmyristate, cyclohexyl ester of tall oil acid, ethyl palmitate, isooctyllaurate, diester of ethylene glycol with stearic acid, tetraester ofpentaerythritol with stearic acid, etc. Likewise useful are esters ofhigher alcohols or commercial alcohol mixtures such as octadecyl alcoholand sperm oil alcohol, and phenols such as phenol, naphthol, p-cresol,and o,pdihexylphenol. The sulfurization is effected most conveniently attemperatures between C. and 250 C. More than one atom of sulfur can beincorporated into the ester by the use of an excess of the sulfurizingagent. For the purpose of this invention sulfurized esters having asmany as 4 or 5 atoms of sulfur per molecule have been found to beuseful. Examples include sulfurized sperm oil having a sulfur content of5%, sulfurized tall oil having a sulfur content of 9%, sulfurized methyloleate having a sulfur content of 3%, and sulfurized stearyl stearatehaving a sulfur content of 15%.

Still another class of the fatty compounds consists of thephosphosulfurized fatty acid ester mentioned above. They are obtained bythe treatment of the esters with a phosphorus sulfide, such asphosphorus pentasulfide, phosphorus sesquisulfide, or phosphorusheptasulfide. The treatment is illustrated by mixing an ester with fromabout 0.5% to 25% of a phosphorus sulfide at a temperature within therange from 100 C. to 250 C. The product contains both phosphorus andsulfur but the precise chemical constitution of such a product is notclearly understood. These and other methods for preparing the sulfurizedesters and phosphosulfurized esters are known in the art.

The polysulfides include principally aliphatic and cycloaliphaticdisulfides, trisulfides, tetrasulfides, pentasulfides, or higherpolysulfides. The term polysulfide designates a compound in which twosubstantially hydrocarbon radicals are joined to a group consisting ofat least 2 sulfur atoms. It is represented for the most part by any ofthe structural formulas below:

Sn R3S-S;.R4; RaSR4,' RaS R4 wherein R and R are alkyl or cycloalkylradicals and n is an integer usually less than 6. The nature of thelinkage between the sulfur atoms is not clearly understood. It isbelieved, however, that such linkage may be described by a singlecovalent bond, a double bond, or a coordinate covalent bond. Thepolysulfides containing at least about 6 carbon atoms per molecule havegreater oil-solubility and are generally preferred. Specific examples ofsuch polysulfides are diisobutyl trisulfide, diisopentyl trisulfide,di-n-butyl tetrasulfide, dicyclopentyl disulfide, dimethylcyclohexyltetrasulfide, di-2-et-hylhexylpentyl disulfide, dipentyl trisulfide,di-beta-pinyl pentasulfide, cyclohexyl cyclopentyl trisulfide,diparaffin Wax trisulfide, di-terpenyl disulfide, didodecyl trisulfide,dibehenyl trisulfide, and diisobutyl hexasulfide. Other polysulfides,including polarsubstituted sulfides, are exemplified bydi(omega-bromopentyl trisulfide.

The preparation of the polysulfide may be accomplished by any of thevarious processes which are known and disclosed in the art including,for example, the reaction of a chlorohydrocarbon with an alkaline metalpolysulfide, the reaction of a mercaptan with sulfur and/ or sulfurhalide, the reaction of saturated and unsaturated hydrocarbons withsulfur and/ or sulfur halides, the reaction of a hydrocarbon monosulfidewith sulfur, etc.

The phosphites useful herein are the diand tri-hydrocarbon esters ofphosphorous acid. Examples of the phosphites are: dibutyl phosphite,diheptylphosphite, dicyclohexylphosphite, tri-(pentylphenyl)phosphite,tris-(dipentylpheny1)phosphite, didecyl phosphite, di-stearyl hosphite,tris-(hexa-propylene-substituted phenyl)phosphite, tri-hexyl phosphite,di-heptyl phenyl phosphite, and tri(mchloro-p-heptylphenyl)phosphite.

The alkaline earth metal salts of the alkylated phenols includeprincipally the salts of magnesium, barium, calcium, and strontium withphenolic substances containing an alkyl substituent having at leastabout 7 carbon atoms. The phenols are exemplified by alkyl phenols,alkyl naphtho'ls, sulfurized alkyl phenols, and the condensationproducts of alkyl phenols with an aldehyde. Specific examples includemagnesium octylphenate, barium polypropylene-substituted phenate inwhich the polypropylene substituent has a molecular Weight of 500,calcium salt of alpha-dodecyl-beta-naphthyl, barium salt ofbis(heptylphenol)sulfide, calcium salt of bis(nonylphenol)sulfide,calcium salt of the condensation product of two moles of heptylphenolwith formaldehyde, barium dodecylphenate, and strontiumpolyisobutene-substituted phenate, in which the polyisobutenesubstituent has a molecular weight of 350.

The esters of the phosphorodithioic acids include the aryl and the alkylesters of the phosphorodithioic acids described hereinabove. Aparticularly useful group of the esters is obtained by the addition ofthe phosphorodithioic acids to an olefinic compound such as an alkene oran aralkene. They are obtained, for example, by the addition ofdiisopropylphosphorodithioic acid with styrene, propene, isobutene,cyclohexene, l-octene, methyl cyclohexene, isoprene, butadiene,dipentene, or the like.

The following examples are illustrative of the lubricating compositionsof this invention (all percentages are by weight):

Example I SAE 20 mineral lubricating oil containing 0.5 of the productof Example 1.

Example II SAE 30 mineral lubricating oil containing 0.75% of theproduct of Example 2 and 0.1% of phosphorus as the barium salt ofdi-n-nonylphosphorodithioic acid.

Example III SAE 10W-30 mineral lubricating oil containing 0.4% of theproduct of Example 3.

Example IV SAE 90 mineral lubricating oil containing 0.1% of the productof Example 4 and 0.15% of the zinc salt of an equimolar mixture ofdi-cyclohexylphosphorodithioic acid and di-isobutylphosphorodithioicacid.

Example V SAE 30 mineral lubricating oil containing 2% of the product ofExample 4.

Example VI SAE 20W-30 mineral lubricating oil containing 5% of theproduct of Example 2.

Example VII SAE 50 mineral lubricating oil containing 3% of the productof Example 5 and 0.1% of phosphorus as the calcium salt ofdi-hexylphosphorodithioate.

Example IX SAE W-30 mineral lubricating oil containing 2% of the productof Example 4, 0.06% of phosphorus as zinc di-n-octylphosphorodithioate,and 1% of sulfate ash as barium mahogany sulfonate.

Example X SAE 30 mineral lubricating oil containing 5% of the product ofExample 1, 0.1% of phosphorus as the zinc salt of a mixture of equimolaramounts of di-isopropylphosphorodithioic acid anddi-n-decylphosphorodithioic acid, and 2.5% of sulfate ash as a basicbarium detergent prepared by carbonating at 150 C. a mixture comprisingmineral oil, barium di-dodecylbenzene sulfonate and 1.5 moles of bariumhydroxide in the presence of a small amount of water and 0.7 mole ofoctylphenol as the promoter.

Example XI SAE 10W-30 mineral lubricating oil containing 6% of theproduct of Example 2, 0.075% of phosphorus as zincdi-n-octylphosphorodithioate, and 5% of the barium salt of an acidiccomposition prepared by the reaction of 1000 parts of a polyisobutenehaving a molecular weight of 60,000 with parts of phosphoruspentasulfide at 200 C. and hydrolyzing the product with steam at C.

Example XII SAE 10 mineral lubricating oil containing 2% of the productof Example 4, 0.075 of phosphorus as the adduct of zincdi-cyclohexylphosphorodithioate treated with 0.3 mole of ethylene oxide,2% of a sulfurized sperm oil having a sulfur content of 10%, 3.5% of apoly- (alkyl methacrylate) viscosity index improver, 0.02% of apoly-(alkyl methacrylate) pour point depressant, 0.003% of a poly-(alkylsiloxane) anti-foam agent.

Example XIII SAE 10 mineral lubricating oil containing 1.5% of theproduct of Example 6, 0.075% of phosphorus as the adduct obtained byheating zinc di-nonylphosphorodithioate with 0.25 mole of 1,2-hexeneoxide at 120 C., a sulfurized methyl ester of tall oil acid having asulfur content of 15%, 6% of a polybutene viscosity index i-rnprover,0.005% of a poly-(alkyl methacrylate) anti-foam agent, and 0.5% of lardoil.

Example XIV SAE 20 mineral lubricating oil containing 1.5% of theproduct of Example 7, 0.5 of di-dodecyl phosphite, 2% of the sulfurizedsperm oil having a sulfur content of 9%, a basic calcium detergentprepared by carbonating a mixture comprising mineral oil, calciummahogany sulfonate and 6 moles of calcium hydroxide in the presence ofan equi-molar mixture (10% of the mixture) of methyl alcohol and n-butylalcohol as the promoter at the reflux temperature.

Example XV SAE 10 mineral lubricating oil containing 2% of the productof Example 2, 0.07% of phosphorus as zinc dioctylphosphorodithioate, 2%of a barium detergent prepared by neutral-izing with barium hydroxidethe hydrolyzed reaction product of a polypropylene (molecular Weight2000) with 1 mole of phosphorus pentasulfide and 1 mole of sulfur, 3% ofa barium sulfonate detergent prepared by carbonating a mineral oilsolution of mahogany acid, and a 500% stoichiometrically excess amountof barium hydroxide in the presence of phenol as the promoter at 180 C.,3% of a supplemental ashless detergent prepared by copolymerizing amixture of 95% (weight) of decyl-methacrylate and 5% (weight) ofdiethylaminoethylacrylate.

Example XVI SAE 80 mineral lubricating oil containing 2% of the productof Example 1, 0.1% of phosphorus as zinc di-nhexylphosphorodithioate,10% of a chlorinated paraffin wax having a ohlorine content of 40%, 2%of di-buty-l tetrasulfide, 2% of sulfurized dipentene, 0.2% of olelylamide, 0.003% of an anti-foam agent, 0.02% of a pour point depressant,and 3% of a viscosity index improver.

Example XVII SAE 10 mineral lubricating oil containing 3% of the productof Example 1, 0.075 of phosphorus as the zinc salt of aphosphorodithioic acid prepared by the reaction of phosphoruspentasulfide with an equimolar mixture of Example XVIII SAE 20 minerallubricating oil containing 2% of the product of Example 2 and 0.07% ofphosphorus as zinc dl-n-ocetylphosphorodithioate.

Example XIX SAE 30 mineral lubricating oil containing 3% of the productof Example 7 and 0.1% of phosphorus as zinc di- (isobutylphenyl-phosphorodithioate.

Example XX SAE 50 mineral lubricating oil containing 2% of the productof Example 7.

Example XXI SAE 90 mineral lubricating oil containing 3% of the productof Example 6 and 0.2% of phosphorus as the reaction product of 4 molesof turpentine with 1 mole of phosphorus pentasulfide.

Example XXII SAE 90 mineral lubricating oil containing 3% of the productof Example 2 and 0.2% of 4,4'-bis-methylene- (2,6-di=tert-butylphenol)Example XXIII SAE 30 mineral lubricating oil containing 2% of theproduct of Example 2 and 0.1% of phosphorus as phenylethyldi-cyclhexylphosphorodithioate.

Example XXIV SAE 90 mineral lubricating oil containing 5% of the productof Example 3 and 1% of the calcium salt of the su-lfurized phenolobtained by the reaction of 2 moles of heptylphen-ol with 1 mole ofsulfur.

The above lubricants are merely illustrative and the scope of inventionincludes the use of all of the additives previously illustrated as wellas others within the broad concept of this invention described herein.

The efiectiveness of the nitrogenand boron-containing compositions asadditives in lubricants to impart oxi dation-inhibiting,corrosion-inhibiting, and detergent properties is illustrated by theresults obtained from an Inhibition-Detergency Test in which a 350-cc.sample of a lubricant containing 0.001% of iron naphthenate and 1.5% byweight of the additive to be tested is heated at 300 F. for 48 hours ina 2 x 15" borosilicate tube. A clean copperlead bearing is immersed inthe lubricant along with an SAE 1020 steel test panel. Air is bubbledthrough the lubricant at the rate of liters per hour. The oxidizedsample is allowed to cool to 122 F. whereupon 0.5% (by volume) of wateris added and dispersed into the sample. The sample is allowed to standfor hours at room temperature and then filtered through dry No. 1Whatman paper (double thickness) under slightly reduced pressure. Theprecipitant is washed with naphtha to constant weight and reported asmilligrams of sludge per 100 ml. of oil. The bearing is scrubbed withnaphtha, dried, and weighed, and the bearing weight change is reportedin milligrams. The viscosity at 100 F. and 210 F. of the lubricantbefore and after the test is noted. Thus, the quantity of sludge is anindication of the ability of the additive to prevent the formation ofharmful deposits; the bearing weight change is an indication of thecorrosiveness of the lubricant; and the viscosity change of thelubricant is an indication of the oxidation resistance of the lubricant.The lubricant base employed in the test is a Mid-Continent,conventionally refined mineral oil having a viscosity 16 of about 200Saybolt Universal seconds at F. The results of the test are summarizedin Table I below.

TABLE I Viscosity Increase, Bearing Sludge Additive (1.5% by weight ofpercent Weight (millidiluent-l'ree chemical change grams per (milli- 100ml. of 100 F. 210 F. grams) lubricant) None 13. 2 3. 1 53. 5 1, Productof Example Q l5. 2 3. 2 1. 7 60 wherein R is selected from the classconsisting of hydrogen and hydrocarbon radicals and R is selected fromthe class consisting of amino, cyano, carbamyl, thiocarbamyl, andradicals having the formulas R N-C(=NR), R NN(R)C(=NR) and NCN(R)C (=NR)and reacting said acylated nitrogen intermediate with a boron compoundselected from the class consisting of boron oxide, boron halides, boronacids, ammonium salts of boron acids, and esters of boron acids in anamount to provide from about 0.1 gram-atomicweight of boron for eachmole of said acylated nitrogen intermediate to about 10gram-atomicweight of boron for each gram-atomic-weight of nitrogen ofsaid acylated nitrogen intermediate.

2. An oil-soluble, nitrogenand boron-containing composition prepared bythe process comprising forming an acylated nitrogen intermediate by thereaction of one equivalent of a substantially aliphatic olefinpolymersubstituted succinic anhydride having at least about 50 aliphaticcarbon atoms in the olefin polymer substituent with at least aboutone-half equivalent of a nitrogen compound selected from compoundshaving the formulas wherein R is selected from the class consisting ofhydrogen and hydrocarbon radicals and reacting said acylated nitrogenintermediate with boric acid in an amount to provide from about 0.1gram-atomic-weight of boron for each mole of said acylated nitrogenintermediate to about 10 gram-atomic-weight of boron for eachgram-atomic-weight of nitrogen of said acylated nitrogen intermediate.

3. The composition of claim 2 wherein the nitrogen compound iscyanoguanidine.

4. An oil-soluble, nitrogenand boron-containing composition prepared bythe process comprising forming an acylated nitrogen intermediate by thereaction of one equivalent of a substantially aliphatic olefin polymersubstituted succinic anhydride having at least about 50 aliphatic carbonatoms in the olefin polymer substituent with at least about one-halfequivalent of a nitrogen compound having the formula and HIIIR' Hwherein R is a carbamyl radical and reacting said acylated nitrogenintermediate with boric acid in an amount to provide from about 0.1gram-atomic-weight of boron for each mole of said acylated nitrogenintermediate to about 10 gram-atomic-Weight of boron for eachgram-atomic-weight of nitrogen of said acylated nitrogen intermediate.

5. The composition of claim 4 wherein the nitrogen compound is urea.

6. An oil-soluble, nitrogenand boron-containing composition prepared bythe process comprising forming an acylated nitrogen intermediate by thereaction at a temperature between about 80 C. and 250 C. of oneequivalent of a polyisobutene substituted succinic anhydride having fromabout 50 to about 250 carbon atoms in the polyisobute-ne substituentwith about an equivalent amount of cyanoguanidine and reacting saidacylated nitrogen intermediate With boric acid in :an amount to provideabout one gram-atomic-Weight of boron for each gram-atomic-weight ofnitrogen of the acylated nitrogen intermediate at a temperature betweenabout 100 C. and 250 C.

7. An oil-soluble, nitrogenand boron-containing composition prepared bythe process comprising forming :an acylated nitrogen intermediate by thereaction at a temperature between about 80 C. and 250 C. of one 18equivalent of a polyisobutene substituted succinic anhydride having fromabout 50 to about 250 carbon atoms in the polyisobutene substituent withabout an equivalent amount of urea and reacting said acylated nitrogenintermediate with boric acid in an amount to provide about onegram-atomic-Weight of boron for each gram-atomic- Weight of nitrogen ofthe acylated nitrogen intermediate at a temperature between about 100 C.and 250 C.

References Cited by the Examiner UNITED STATES PATENTS 2,052,192 8/1936Piggott 260404 2,216,618 10/1940 Katz 260-401 2,234,581 3/1941 Rosen252-51 2,611,746 9/1952 Kipp 252-496 3,087,936 4/1963 Le Suer 252-51.5

ALEX MAZEL, Primaly Examiner.

20 DANIEL E. WYMAN, HENRY R. JILES, Examiners.

P. P. GARVIN, J. TOVAR, Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,281,428 October 25, 1966 William M. Le Suer It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

Column 1, line 67, for "iwth" read with column 3, line 71. for "such as"read such a column 7, line 24, for "proportionss" read proportionscolumn 10, line 21, for "cyclalkanes" read cycloalkanes column 14, line67, for "olelyl" read oleyl column 15, line 9, for"din-ocetylphosphorodithioate" read di-n-octylphosphorodithioate column16, line 19, for "substitute" read substituent Signed and sealed this15th day of October 1968,

SEAL) LttCStI dward M. Fletcher, Jr. EDWARD J. BRENNER Ittesting OfficerCommissioner of Patents

1. AN OIL-SOLUBLE, NITROGEN- AND BORON-CONTAINING COMPOSITION PREPAREDBY THE PROCESS COMPRISING FORMING AN ACYLATED NITROGEN INTERMEDIATE BYTHE REACTION OF ONE EQUIVALENT OF A SUBSTANTIALLYHYDROCARBON-SUBSTITUTED SUCCINIC ACID-PRODUCING COMPOUND HAVING AT LEASTABOUT 50 ALIPHATIC CARBON ATOMS IN THE SUBSTANTIALLY HYDROCARBONSUBSTITURE WITH AT LEAST ABOUT ONE-HALF EQUIVALENT OF A NITROGENCOMPOUND HAVING THE FORMULA